JPH0726342B2 - Painting method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for painting various molded articles coated with a polyester resin such as polybutylene terephthalate (PBT) copolymer and polyethylene terephthalate (PET) copolymer. .

More specifically, the present applicants previously filed various coated articles manufactured by "Coating method for molding material" (Japanese Patent Application No. 61-294384), and various metal articles coated with polyester resin, and , A method for painting various polyester resin molded articles reinforced with glass fiber, carbon fiber, etc. By applying the painting method of the present invention, it becomes possible to attach a variety of colors or a variety of patterns to the whole or a part of the article, thereby enhancing the commercial value.

(Prior Art) A polyester resin-coated molded article manufactured according to Japanese Patent Application No. 61-294384 has a ceramic-like prominent appearance, the surface is glossy and does not easily get dirty, and it has impact resistance. It has excellent characteristics such as being large.

Usually, when painting ceramics, the method of forming a pattern on the glaze, glaze (in glaze), or glaze by firing at high temperature using an inorganic pigment (mainly metal oxide) It is common. However, due to subtle differences in firing conditions (temperature, atmosphere, etc.), there are problems that the desired color may not be finished, or that a bright color may be difficult to produce. Therefore, it required skill to perform constant painting and constant painting. In addition, the pattern formed on the glaze and the glaze is very strong, but the color usage is limited, and the pattern formed on the glaze is relatively free of color usage, but it is inferior in durability etc. There is.

Furthermore, because of the high-temperature firing, the molded articles must shrink or distort, and consume a large amount of energy, such as ornaments excluding some high-quality works of art, food-related containers, daily necessities, tools, etc. The above method is not necessarily suitable for painting.

Also, organically fix the pigment on the glaze, dry it,
There is also a method of painting by baking at low temperature, but it is not suitable for painting the above-mentioned article because it is not in the glaze state.

(Problems to be solved by the invention) Since the above-mentioned polyester resin-coated molded articles such as PBT copolymers and PET copolymers have a pottery-like appearance, if coloring with a dye is used as the painting method, It is not limited to use, and it can be finished as if it was painted with Inglaze, increasing the commercial value. However, due to the smoothness and denseness of the polyester coating, cissing and sagging occur, and coloring with a dye is very difficult.

For example, even if a printing paste of a usual polyester fiber dyeing recipe is used for coloring with a disperse dye, color unevenness and bleeding easily occur due to the above-mentioned cissing and sagging, and satisfactory painting cannot be performed. Conventionally, since there is no prior art or publicly known example of such a painting method, the inventors of the present invention have made diligent studies on a dye liquid that is well compatible with a polyester resin having a smooth surface and a dense surface, and as a result, as a surfactant, a fluorine-based surfactant is used. It was found that a beautiful painting can be made on the article by coloring with a dye solution containing
The present invention has been reached.

That is, the gist of the present invention is that when the surface of a polyester resin-coated molded article is colored with a dye solution consisting of a disperse dye, a sizing agent, a fluorosurfactant, and an auxiliary agent and heated to fix the dye, a fluorosurfactant is used. 0.00005〜 in 100 parts by weight of dye solution
This is a method for painting a polyester resin-coated molded article, characterized by using 0.0003%. Using the method of the present invention,
Smoothness of the surface due to the wetting effect of the fluorinated surfactant,
The surface of the article, which is difficult to be colored due to the denseness and the like, can be easily colored in various ways by a method such as writing, spraying, dipping, and printing. Further, it is not necessary to carry out a treatment at a high temperature such as firing, and the disperse dye can be fixed only by heating at a relatively low temperature for a short time.

As the disperse dye, dyes usually used for printing polyester fibers can be used. Aminobenzene-based dyes are used as yellow and red dyes, aminoanthraquinone dyes are used as purple and blue dyes, and nitrodiaryl dyes and quinophthalone are used as yellow dye dyes. The thing of a system is typically used.

It is natural to select and use one of these dyes that develops color at the lowest temperature.

The amount of the dye used is appropriately 1 to 20 parts by weight in 100 parts by weight of the dye solution.

As the sizing agent component in the dye solution, any adhesive can be used as long as it has good adhesion to the polyester resin film, excellent leveling, and is easy to wash the remaining sizing agent with water after fixing the dye by heating. Although an acrylic ester aqueous solution, a sodium alginate aqueous solution, or an O / W type half emulsion paste composed of water and turpentine oil is preferably used, it is also possible to use. These can be used alone, but can be used in combination.

Next, a fluorochemical surfactant and, if necessary, an auxiliary agent are added to and mixed with the mixture of the disperse dye and the sizing agent to prepare a dye solution. At this time, the fluorochemical surfactant is mixed with the dye solution. Add 0.00005 to 0.0003% in 100 parts by weight.

By adding the fluorine-based surfactant, the surface tension of the dye solution can be lowered, so that the cissing phenomenon described above can be prevented and the polyester coating can be smoothly colored. However, if the amount of the fluorine-based surfactant added is less than 0.00005, the cissing phenomenon cannot be sufficiently prevented, and the amount of 0.0003%
On the contrary, if it exceeds the range, wetting becomes too good, which causes sagging and prevents the dye from accommodating to the coating, which is not preferable. As the fluorosurfactant, one having a fluoroalkyl group having 6 to 10 carbon atoms or a perfluoroalkyl group as a hydrophobic group is used. C6-10 as hydrophobic group
Examples of the surfactant having a fluoroalkyl group include fluoroalkylcarboxylic acids, and for example, tetradecafluorocaprylic acid, hexadecafluoropelargonic acid and the like are preferably used. Examples of the surfactant having a perfluoroalkyl group having 6 to 10 carbon atoms as a hydrophobic group include perfluoroalkylcarboxylic acid and its salt,
Examples include perfluorooctanecarboxylic acid and potassium perfluorooctanecarboxylate. Further, perfluoroalkylsulfonic acid, its salt, and its derivative are also preferably used, and perfluorooctanesulfonic acid, lithium perfluorooctanesulfonic acid, perfluorooctanesulfonic acid diethanolamide, sodium N-perfluorooctanesulfonylglutamate, perfluorooctanesulfonic acid Examples include fluorooctane-N-ethylsulfonylglycine potassium, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluorooctanesulfonamidopropyltrimethylammonium and the like. In addition, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluorooctylethyltin acid ester, sodium 3- [fluorooctyloxy] -1-propylsulfonate, 3- [ω-fluoro Octanoyl-N-ethylamino] -1 sodium propanesulfonate, N- [3- (perfluorooctanesulfonamido) propyl] -N, N
-Dimethyl-N-carboxymethylene ammonium betaine and the like are preferably used.

The dyeing liquid thus obtained, within a range that does not hinder the familiarity with the polyester film, a printing paste used for dyeing polyester fibers, for example, starch, CM
It is also possible to use C, PVA, etc. together. Examples of the auxiliaries include acids, dye-improving agents, defoaming agents, etc., which are used in ordinary polyester fiber printing pastes. For example, acids include tartaric acid, citric acid, succinic acid, and the like. As the adhesion-improving agent, a phenylphenol-based agent, a methylnaphthalene-based agent, a chlorobenzene-based agent, or the like, and a defoaming agent such as a higher alcohol-based agent can be applied.

As a method for coloring the dye solution thus obtained on the polyester-coated molded article, there are methods such as a brush, a spray, a screen, printing, dipping, and a pad.
A method most suitable for the shape or pattern of the article may be adopted.

The article colored as described above is then heated to fix the dye. The temperature is preferably 70 to 170 ° C., and the treatment time is suitably 1 to 30 minutes.

When the temperature is lower than 70 ° C, the adhesion is not sufficient, and when the temperature is higher than 170 ° C, the polyester coating melts. Similarly, if the treatment time is shorter than 1 minute, the fixation is not sufficient, and if it exceeds 30 minutes, the effect associated therewith cannot be obtained, and the characteristics of the coating are adversely affected, which is not preferable.

An apparatus for performing the above heat treatment is not particularly limited, but a heating furnace is usually used industrially.

The polyester resin-coated molded article which has been subjected to the heating step and which has been painted is washed as it is or washed with water to remove the remaining components and dried to obtain a finished product.

The polyester film-molded articles to be painted in the present invention are various articles obtained by the applicant's patent application for a method for coating a molded article material (Japanese Patent Application No. 61-294384). , Polyester resin by powder coating method such as fluidized dipping method, electrostatic coating method, etc. by molding raw materials such as various stone powders, porcelain clay, porcelain stones, kaolin, raw materials for fine ceramics, etc. It is an article coated with.

Further, the painting method of the present invention can be applied to molded articles such as rods, plates, pipes, molded articles and the like coated with a thermoplastic polyester resin. These molded articles include general ornaments, food-related containers, daily necessities, tools, etc. Specifically, jars, lamp stands, dolls, character products, bonbon cases, decorative dishes, demon tiles, svenil, console sets. , Butter case, jam jar, mixing ball,
For example, tiles.

Furthermore, the painting method of the present invention can also be applied to various polyester resin molded articles reinforced with glass fibers, carbon fibers and the like.

(Examples) The present invention will be described in more detail with reference to examples.

Production Example 1 10 parts by weight of titanium dioxide was added to 100 parts by weight of a polyester copolymer obtained by copolymerizing a dicarboxylic acid containing 55 mol% of terephthalic acid and 45 mol% of isophthalic acid, and 1,4-butanediol. The mixture was added, uniformly mixed, and then pulverized to obtain a polybutylene terephthalate copolymer resin powder having an average particle diameter of about 150 microns. This was preheated at 370 ℃ for 10 minutes, and the material was made by kneading and drying clay (10 cm tall tiger figurine, 30 cm tall vase, 10 cm square tile, 15 cmφ)
A plate or the like) or a steel plate (75 × 150 × 1 mmt) was coated on the surface by a fluidized-bed method, and if necessary, post-heated at 190 ° C. or 200 ° C. for 1 minute to obtain various polyester resin-coated molded articles.

Example 1 Acrylic ester aqueous solution (trade name Primal P-6
N, manufactured by Nippon Acrylic Chemical Co., Ltd., solid content 25%) 20 parts by weight (hereinafter, simply referred to as "part") was dissolved in 70 parts of water to prepare a paste. Disperse dye paste (brand name Ceracolor / red,
Hayashi Chemical Industry Co., Ltd., dye: dispersant: water = 1: 1: 1 mixture, dispersant Orotan SN, used by Rohm and Haas Co.) 1
0 part was added, and then 1 part of a fluorine-based surfactant (trade name: Florard FC-129, containing 1% of potassium salt of perfluoroalkylcarboxylic acid manufactured by 3M) was added and mixed well to prepare a dye solution. This dye solution was spray-painted on the white 10c square tile obtained in Production Example 1. After painting
Tile was held vertically and observed for dripping and cissing, but they were not seen and the coated surface was smooth. The dyed tiles were then fixed by heating the colored tiles at 120 ° C for 10 minutes.
After cooling, it was washed with water to remove excess sizing agent to obtain a colored tile painted in good red color.

Example 2 As a sizing agent, the following components were prepared: Primal P-6N 10 parts Sodium alginate ^* (2% aqueous solution) 10 parts Water 70 parts Total 90 parts (* made by Kelco, USA) and dispersed therein. Dye paste (cera color / blue,
A dye solution was prepared by adding 10 parts of the same composition as in Example 1) and finally adding 1.0 part of a fluorinated surfactant (Florard FC-129) and mixing them well. This was spray-coated in the same manner as in Example 1 and heated at 120 ° C. for 10 minutes to fix the dye. No cissing or sagging was observed during painting, and the sizing agent was easily removed after heating, and a colored tile painted in good blue was obtained.

Example 3 As a sizing agent, the following components were prepared: Primal P-6N 17 parts Sodium alginate (3% aqueous solution) 68 parts A total of 85 parts were prepared, and a disperse dye paste (Ceracolor / green, composition is the same as in Example 1). ) Was added 15 parts. Furthermore, 0.75 parts of a fluorine-based surfactant (Florard FC-129) was added and mixed well to prepare a dye solution. Using this, a green pattern was drawn by writing on the white 30 cm-high vase obtained in Production Example 1. At that time, there was no repelling, thin lines could be clearly expressed, and there was no blurring. Then, the dye was fixed by heating at 90 ° C. for 20 minutes. After cooling, it was carefully washed with water to obtain a vase on which a pattern with thin green lines was painted.

Example 4 Ceracolor / Yellow (the composition is the same as in Example 1) was used as the disperse dye paste, and a 1% solution of Futagent 100 (perfluoroalkyl sulfonate, manufactured by Neos Co., Ltd.) as the fluorosurfactant. A dye solution was prepared under the same conditions as in Example 1 except that (the solvent was an equal mixture of water and ethanol). This dye solution was spray coated on the white steel plate (75 × 150 × 1 mmt) obtained in Production Example 1. After painting
When the steel plate was held vertically, sagging and cissing were observed, but they were not seen and the coated surface was smooth. Then, the colored steel sheet was heated at 110 ° C. for 15 minutes to fix the dye. After cooling, the product was washed with water to remove excess sizing agent to obtain a colored steel plate with a good yellow color.

Example 5 A sizing agent having the same components as in Example 3 was used, and Ceracolor / Black (the composition is the same as that in Example 1) was used as a disperse dye paste.
15 parts, 0.75 of a 1% solution of Futergent 100 as a fluorosurfactant (solvent is an equal mixture of water and ethanol)
Part of the mixture was added and mixed well to obtain a dye solution. Using this, a black pattern was drawn on the white 15 cmφ dish obtained in Production Example 1 by writing. At that time, there was no repelling and thin lines could be clearly expressed. Then, the dye was fixed by heating at 100 ° C. for 20 minutes. After cooling, the plate was carefully washed with water to obtain a dish on which a pattern with thin black lines was painted.

Example 6 First, the white tiger figurine having a height of 10 cm obtained in Production Example 1 was prepared as in Example 4.
The whole was colored yellow by spray coating using the yellow dye obtained in the above formula. After left at room temperature for about 1 hour to dry, a striped pattern was drawn on the yellow background by writing with the black dye solution obtained in the formulation of Example 5 by brush writing. At that time, phenomena such as cissing and sagging were not observed, and a desired design could be drawn. The tiger ornament colored in this way was heated at 120 ° C. for 10 minutes to fix the dye. After cooling, the product was washed with water to remove excess glue, and a beautiful tiger figurine with a striped pattern was obtained.

Comparative Example 1 The following components as a sizing agent, Was prepared, and 20 parts of the disperse dye paste (Ceracolor / red) was added and mixed without using a fluorosurfactant to prepare a dye solution. 15cmφ obtained in Production Example 1 using this
I drew a pattern on the plate by writing. The dye solution was repelled by the polyester resin film, and bleeding occurred on both edges of the line, making it impossible to draw a fine line. Then at 90 ℃ 10
The dye was fixed by heating for a minute. After washing the remaining sizing agent with water, the pattern was examined, but many shades of color, blurring, and blemishes were seen, and satisfactory painting could not be performed.

Comparative Example 2 As a sizing agent, a mixture of 80 parts of starch paste and 10 parts of water was used, and 10 parts of a disperse dye paste (Ceracolor / green) was added.
A dye solution was prepared by mixing without using a fluorine-based surfactant. Using this, a pattern was drawn in the same manner as in Comparative Example 1, but sagging was observed in addition to the cissing phenomenon, and coloring by handwriting was very difficult. The dye was fixed by heating at 100 ° C for 10 minutes, but the fixing property was poor, and painting with commercial value could not be performed.

(Effects of the Invention) By carrying out the method of the present invention, the following effects are achieved.

A wide variety of paintings can be made using various disperse dyes.

Painting is done at low temperature (70-170 ℃), so vivid coloring is possible.

There is no shrinkage or distortion of the substrate often seen in the conventional method of coloring by high temperature firing.

A large amount of energy consumption associated with high temperature firing is avoided.

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Claims (6)

[Claims] 1. A fluorosurfactant when the surface of a polyester resin-coated molded article is colored and heated with a dye solution comprising a disperse dye, a sizing agent, a fluorosurfactant, and an auxiliary agent to fix the dye. 0.0005 to 0.0003% in 100 parts by weight of a dye solution. 2. The hydrophobic group of the fluorosurfactant has 6 to 6 carbon atoms.
The painting method according to claim 1, wherein the fluoroalkyl group is 10. 3. The hydrophobic group of the fluorosurfactant has 6 to 6 carbon atoms.
The painting method according to claim 1, wherein the painting method is 10 perfluoroalkyl groups. 4. The painting method according to claim 1, wherein heating is performed at a temperature of 70 to 170 ° C. for 1 to 30 minutes. 5. The painting method according to claim 1, wherein the polyester resin is a polybutylene terephthalate copolymer. 6. The painting method according to claim 1, wherein the polyester resin is a polyethylene terephthalate copolymer.